Process of treating hydrocarbon oils and bituminous materials



A. FISHER 2,010,357

PROCESS OF TREATING HYDROCARBON OILS AND BITUMINOUS MATERIALS Aug. 6,1935.

Filed Feb. 21, 1950 fzifenior. fllfred fisher, J27

ldztness Patented Aug. 6, 1935 UNITED STATES PATENT OFFICE PROCESS OFTREATING HYDROCARBON OILS AND BITUMINOUS MATERIALS Alfred Fisher,Chicago, Ill., assignor to Universal Oil Products Company, Chicago,Ill., a corporation of South Dakota Application February 21, 1930,Serial No. 430,200

4 Claims.

' conversion of various mixtures of bituminous material such as variouscoals, lignites, peats, tars, pitches,- etc., with liquid hydrocarbonstogether with other substances in a dispersed or emulsified form atelevated temperatures with or without the use of catalysts so as toproduce lower boiling point hydrocarbons and coke.

Among the objects of my invention is the utilization of low grade coalsand coal wastes as well as the higher grade coals in the treatment ofmixtures of oil and the bituminous materials for the production of ahighly anti-knock motor fuel. Coal breeze and fines which are usually ofthe lowest economic value or constitute a waste are especially suitablefor processing according to the method of my invention. This materialbeing all ready resolved to a fine state of division does not requiremuch further pulverization to treat by my process. These materials aswell as lignites, tars, pitches, gilsonite, grahamite, Montan wax,shales and the like, or mixtures thereof, are treated to produce a cokeand a maximum yield of lower boiling point hydrocarbons.

The bituminous materials processed in the presence of the hydrocarbonsare substantially deprived of their hydrocarbon content anddevolatilized in the process of my invention so that the coke from thebituminous material is intimately mixed and consolidated with the oilcoke. A coke product results which has for the main part sufiicientbody, strength and burning qualities so that no briquetting treatment isordinarily required.

Among further objects of my invention is to provide a process wherebituminous materials and hydrocarbon oils aresimultaneously convertedand carbonized in one operation or step rather than in separate steps asin the carbonization process and in the separate cracking of the tarproducts from the carbonization operation. In-

creased yields and improved products result from the carbonization ofthe several operations with a minimum formation of gaseous products.

My invention in its specific embodiment consists in the use ofstabilizing means when :processing mixtures of bituminous materials andhydrocarbon oils so that suspensions of such ma-' terials will notseparate prior to their introduction into the process or during theprocess. Suspension of such materials would ordinarily the maintainedprior to introduction into the conversion plant by some form ofagitation. After introduction into the plant, maintenance of thesuspension would be dependent on physical factors such as velocityconditions, turbulence, proportions of the components, relative specificgravity, surface tension, etc., factors which assume little importancein maintaining uniform and stable mixtures in my process. Advantagesresult from the stabilization of these mixtures as carried out in myinvention since in addition to stabilizing same, the suspensions retaintheir uniformity and are in a suitable condition to also maintain insuspension catalytic materials which, in many cases even though in veryfinely divided state, are heavy and readily separated out.

The stabilization is brought about by the use of a paste consisting ofan admixture of colloidal clay and water into which a salt is preferablyincorporated which, when emulsified with the oil, will prevent the oilsuspension containing dispersed coal from breaking. Other stabilizingagents, such as soaps, gums, glues, etc. may be used alone or inconjunction with the clay. The incorporation of a soluble salt, such aszinc chloride, for example, causes a thickening of the oil mixture andassists in the stabilization of same. Some salts added for this purposealso exert a catalytic eifect upon the subsequent conversion reaction.When other catalysts are used, the emulsion assists in stabilizing theresulting suspension. The proportion or quantity of bituminous materialswhich can be admixed with the oil in this manner depends on the finenessof pulverhydrocarbon oils as above prepared to cracking or conversionconditions at elevated temperaturesv in some, form of conversionapparatus of which the attached drawing is an illustration.

Temperature conditions used, at the outlet of the heating element mayvary from 700 to 1200 F., and pressures may vary from atmospheric tohigh super-atmospheric pressures.

Pressure-on the balance of the system may vary from sub-atmospheric oratmospheric pressure to high super-atmospheric pressures.

Referring now to the attached drawing, the

stabilized suspension of bituminous material in hydrocarbon oil isintroduced through line I and valve 2 and pumped by means of pump 3through line 4 and valve 5, with valve 6 in line I closed, into line 8where it mixes with hot refiux oil being pumped from the dephlegmator.This mixture of materials to be processed then passes into the heatingelement 9 located in the heating zone 10, the heating element being ofsuch design as to process the oil suspension at suitable time,temperature, pressure and velocity conditions. The heated materials orproducts therefrom leave the heating zone through line H and valve l2and enter the reaction zone 13 where the reaction continues andvaporization and separation or deposition take place. Materialswithdrawn from this reaction zone during the period when the process isbeing brought to operating conditions or removed during the operationare withdrawn through line l4 regulated by valve l5 which may lead tostorage or to suitable processing elements not shown. The vaporous andgaseous products leave the reaction zone through line 16 and valve I1,and enter near the bottom of a dephlegmating zone l8 where the vaporsmay be subjected to heat interchange and cooling. The reflux condensateand any materials added flow downward through the line 19 and valve 20to the suction side of hot oil pump 2| from which they are pumpedthrough line 8 to mix with fresh materials and be reprocessed. Thevapors and gases leaving the dephlegmator l8 pass through the line 22and valve 23 to the condenser and/or cooler 24 and the cooled productsthen flow through line 25 and valve 26 into the receiver 21 whereseparation of the liquid and uncondensed vapors and gases is efiected.The gases and uncondensed vapors leave the system through line 28regulated by valve 29 and the liquid product containing motor fuelhydrocarbons is withdrawn through line 30 regulated by valve 3|. Wateris withdrawn through line 50 regulated by valve 5|. Regulated portionsof the oil product produced in the receiver 21 may be discharged throughthe line 32 and valve 33 to the suction side of pump 34 which pumps thisoil through line 35 and valve 36 to the top of dephlegmator l8. Duringthe starting up period or in the progress of the operation, hydrocarbonoil may be introduced through line 31 and valve 38 to the suction sideof pump 39 from which it is pumped to the dephlegmator through lines 40and 4|, valve 42 being open and valve 43 in line 40 being closed. A partof the flow of the hydrocarbon oil may be directed to the heatingelement 9 by partly opening the valve 43 and with suitable adjustment ofvalve 42 allowing said oil to fiow through line 40 and valve 44 intolines 4 and 8, the valve 45 in line 45 being closed, or the whole flowof the hydrocarbon oil may be pumped directly to the heating element byclosing valve 42 and opening valve 43. In the event that it may be sodesired, a portion or all of the oil may be directed through line 46 andvalve 45 into the line I from which it can be directed into line I Ibefore or after valve l2 by the obvious regulation of either valve 41 inline 48 or valve 49. In a like manner, any desired portion of thestabilized suspension of bituminous material in hydrocarbon oil may bepumped by pump 3 through line 4 and directed, if so desired throughvalve 6 in line 1 into the line H.

As a specific example of the application of the method of my inventionand the results obtained, a smooth paste prepared from approximately onepart of clay and 10 parts of water was agitated with approximately 14 to16 times its own volume of 28-30 degrees A. P. I. gravity topped Mid-Continent crude oil and incorporated into same forming an emulsion. Thisemulsion was then stabilized by further agitation and the addition ofapproximately 34% of a 16 Baum zinc chloride solution, when a pronouncedthickening effect was observed. Approximately 50% of powdered Illinoisbituminous coil Was then stirred in and agitated with the emulsified oiland a stable, uniform and intimate suspension obtained. This productwhen used as a charging material to the process and treated in theheating coil together with recycled oil from the process so that thetemperature and pressure at the heating coil outlet is approximately 920degrees F., and 400 pounds should give the following results with anoperation of the non-residuum type i. e. where there is no removal ofnon-vaporized oil from the reaction chamber after the process has beenbrought on stream and operating conditions fully established. In suchoperation the pressure is reduced in the line from the heating coil tothe reaction chamber to approximately 125 pounds. The vapors from thereaction chamber are dephlegmated and partially converted hydrocarbonscondensed and returned to the heating zone as recycled oil. Thetemperature at the top of the dephlegmator is maintained at about 450degrees F., by recirculation of the end oil product. The pressure on thereaction, dephlegmation, condensing and collecting zones is regulated bymaintaining a liquid level in the receiver and the release of theuncondensable gases formed during the operation.

The above described operation may be started and brought tosubstantially normal conditions of operating pressure and temperature byprocessing separately the 28-30 gravity topped crude only. This periodcovers a space of approximately 3 hours.

The blended coal and oil coke product removed from the chamber at theend of the run would be a broken agglutinated mass, quite dry, not quiteas hard as petroleum coke and lacking to some extent in its honey-combstructure. The volatile content of the coke blend would be approximately16% and the calorific value, about 13,500 B. t. u. per pound.

The distillate from the process would contain approximately 73% of 418end-point motor fuel. The composite motor fuel would have an antiknockvalue equivalent to approximately 40% of benzol in Pennsylvania straightrun gasoline. The distillate is calculated to be produced from the coalat the rate of approximately 12 gallons per ton and approximately 78%based on the topped crude oil processed. Yields of approximately 35% ofmotor fuel may be made from the mixture at the conditions of the aboveexample.

My invention should not be construed as being limited to the exampleswhich I have shown, or the-particular components and proportions ofmaterials used, or the specific manner of preparation which I have givenonly by way of illustration since within the scope of the invention,there are many combinations and modifications that may be employed.

I claim as my invention:

1. A process of treating substantially solid comminuted pyro-bitumen,which consists in mixing said pyro-bitumen with an emulsion of water andoil containing zinc chloride and an emulsifying agent, and thensubjecting such mixture to temperature sufiicient to decompose the sameand comminuted pyro-bitumen, which consists in mixing said pyro-bitumenwith an emulsion of water and oil containing zinc chloride and anemulsifying agent, and then subjecting such mixture to temperature andpressure sufficient to decompose the same and produce therefromrelatively low boiling hydrocarbons.

3. A process for treating hydrocarbon oil and solid pyro-bituminousmaterial which comprises admixing the pyro-bituminous material in finelydivided form with the oil, converting the mixture into a suspension bythe incorporation of an emulsifying agent thereinto, thickening andstabilizing the suspension by adding zinc chloride thereto, subjectingthe suspension to cracking conditions of temperature and pressure andseparating the same into vapors and unvaporized residuum, and condensingthe vapors.

4. A process for treating hydrocarbon oil and ,solid pyro-bituminousmaterial which comprises admixing the pyro-bituminous material in finelydivided form with the oil, incorporating a paste of colloidal clay andwater into the mixture to form a. suspension, thickening and stabilizingthe suspension by the addition of zinc chloride, subjecting thesuspension to cracking conditions of temperature and pressure andseparating the same into vapors and unvaporized residuum, and condensingthe vapors.

ALFRED FISHER.

